SAB 4923 Advanced Water and Wastewater Treatment Chemical Precipitation

CHEMICAL PRECIPITATION
Definition:Removal of metal ions from solution by changing the solution composition, thus causing the metal ions to form insoluble metal complexes.

Applications Removal of metals from waste stream Treatment of hard water Phosphorus removal Theory of Chemical Precipitation Solubility equilibria:A chemical reaction is said to have reached equilibrium when the rate of forward reaction is equal to the rate of the reverse reaction

Equilibrium constant, where: a, b, c, d () stoichiometry coefficients equilibrium activities. For dilute concentration, molar concentration is used to approximate activities value. By convention, the activities of solid material (such as precipitates) and solvent (such as water) are taken as unity, (1).

For dissolution of solid materials,

Due to dilute concentration, Ksp = [A+] [B-] = solubility product constant where [ ] refer to molar concentration
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Azmi Aris 2011

SAB 4923 Advanced Water and Wastewater Treatment Chemical Precipitation

For a more general dissolution reaction:

Thus,

The value of solubility product constant gives some indications of the solubility of a particular compound. if [Ay+]x [Bx-]y < Ksp if [Ay+]x [Bx-]y > Ksp : no precipitation will occur : precipitation will occur

Table 1 Solubilities of several compounds Compound CaCO3 CaCl2 Ca(OH)2 CaSO4 Mg(OH)2 Solubility at 25oC, mg/L 18 745000 770 1620 40 Ksp 5 x 10-9 159 x 106 8 x 10-6 2 x 10-5 9 x 10-12

Basic Principles: A. B. C. D. Add chemical precipitants to waste stream Mix thoroughly Allow solid precipitates to form floc by slow mixing Allow floc to settle in clarifier

Azmi Aris 2011

SAB 4923 Advanced Water and Wastewater Treatment Chemical Precipitation

Figure 1 Chemical precipitation flow diagram Heavy Metal Removal Apply to industrial wastewaters such as from plating and polishing operations, mining, steel manufacturing, electronics manufacturing Metals include arsenic, barium, chromium, cadmium, lead, mercury, silver Types of precipitation Hydroxide precipitation Sulphide precipitation Carbonate precipitation Hydroxide Precipitation Add lime or sodium hydroxide to waste stream to precipitate heavy metals in the form of metal hydroxides. CaO in the form of slurry while NaOH in the form of solution. NaOH is easier to handle but is very corrosive. Will form floc and settle in clarifier

Azmi Aris 2011

SAB 4923 Advanced Water and Wastewater Treatment Chemical Precipitation

Sulphide Precipitation Use of sulphide in the form of FeS, Na2S or NaHS Better metal removal as sulphide salt has low solubility limit Limitation: can produce H2S (g) at low pH At low pH, reaction will proceed to the right. Thus, require pH > 8 for safe sulphide precipitation. Carbonate Precipitation Use of carbonate in the form of Na2CO3 Equilibrium Consideration A precipitate will form when two solutions are mixed if and only if the concentration of the metal ions is greater than the solubility of the ions in solution for the particular solution composition

Figure 2 Residual metals concentration using Na2CO3 precipitation

Azmi Aris 2011

SAB 4923 Advanced Water and Wastewater Treatment Chemical Precipitation

Figure 3 Heavy metal precipitations as the hydroxide and the sulphide

Additional Notes Need of preliminary treatment in the presence of interference eg. cyanide and ammonia Enhanced removal may require coprecipitation or filtration after clarification

Azmi Aris 2011

SAB 4923 Advanced Water and Wastewater Treatment Chemical Precipitation

Example 1: One litre of an aqueous wastewater containing 10-4 moles/L Zn2+ is treated by hydroxide precipitation at pH=10 (Atomic weight of Zn = 65.4 g/mol) Zn2+ + Ca(OH)2 Zn(OH)2 + Ca2+ 1. 2. 3. 4. Will a precipitate form? What will the equilibrium composition of the solution be in the presence of the precipitate? What is the % Zn removed from the solution? What could be done to improve the treatment?

Azmi Aris 2011

SAB 4923 Advanced Water and Wastewater Treatment Chemical Precipitation

Water Softening Hardness is caused by Ca2+, Mg2+, Fe2+, Mn2+, Sr2+ and Al3+ + Carbonate hardness caused by anion CO3-2, HCO3+ Non-carbonate hardness caused by anion SO4-2, Cl+ Level of Acceptance Soft : Moderately hard : Hard : Very hard : + Problems Interfere with laundering excessive soap consumption Scale production in hot-water heaters and pipes Objective of water softening is to remove hardness in water by removing Ca2+ and Mg2+ Chemical precipitation using lime (CaO) or lime slurry (Ca(OH)2) and soda ash (Na2CO3)

Chemical Reactions Carbonate Hardness Reaction of lime with existing CO2 in water CO2 + Ca(OH)2 = CaCO3 + H2O Reaction of lime with bicarbonate Ca(HCO3)2 + Ca(OH)2 = 2CaCO3 + 2H2O Conversion of HCO3- to CO3-2 Mg(HCO3)2 + Ca(OH)2 = CaCO3 + MgCO3 + 2H2O Precipitation of Mg2+ MgCO3 + Ca(OH)2 = Mg(OH)2 + CaCO3 Non-carbonate Hardness Precipitation of Mg2+ MgSO4 + Ca(OH)2 = Mg(OH)2 + CaSO4 MgCl2 + Ca(OH)2 = Mg(OH)2 + CaCl2 Precipitation of Ca2+ by soda ash (Na2CO3) CaSO4 + Na2CO3 = CaCO3 + Na2SO4 CaCl2 + Na2CO3 = CaCO3 + 2NaCl (3.6-5) (3.6-6) (3.6-7) (3.6-8) (3.6-1) (3.6-2) (3.6-3) (3.6-4)

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SAB 4923 Advanced Water and Wastewater Treatment Chemical Precipitation

Process Variations in Lime-Soda Ash Softening Three types of variations: Excess lime softening Selective calcium carbonate removal Split-treatment softening Excess lime treatment Removal of Ca2+ and Mg2+ hardness to the practical limit of CaCO3 solubility by stoichiometric additions of lime (Eqn. 3.6-2). The practice is to reduce the total hardness to 40 mg/L of CaCO3 (i.e. 30 mg/L of CaCO3 and 10 mg/L of Mg2+ hardness) Precipitation of Mg2+ requires a surplus of 35 mg/L of CaO above stoichiometric requirements. After excess-lime treatment, water is scale-forming and must be neutralised. This is carried out using CO2 (recarbonation) and soda ash.

Azmi Aris 2011

SAB 4923 Advanced Water and Wastewater Treatment Chemical Precipitation

Example 2: Water defined by the following analysis is to be softened by excess lime treatment. Assume that the practical limit of hardness removal for CaCO3 is 30 mg/L and that of Mg(OH)2 is 10 mg/L as CaCO3. CO2 Ca2+ Mg2+ Na+ = = = = 8.8 mg/L 40.0 mg/L 14.7 mg/L 13.7 mg/L Alk (HCO3-) SO42Cl= = = 135 mg/L as CaCO3 29.0 mg/L 17.9 mg/L

a. Sketch a meq/L bar graph and list the hypothetical combinations of chemical compounds in solution. b. Calculate the softening chemicals required required expressing lime dosage as CaO and soda ash as Na2CO3. c. Draw a bar graph for the softened water before and after recarbonation. Assume that half the alkalinity in the softened water is in the bicarbonate form.

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SAB 4923 Advanced Water and Wastewater Treatment Chemical Precipitation

Selective calcium carbonate removal To soften water low in Mg2+ hardness (< 40 mg/L as CaCO3). No excess lime for Mg2+ removal. One step recarbonation. Soda ash may or may not be required depending on the extent of noncarbonate hardness. If CaCO3 precipitate does not settle satisfactorily, coagulant aid or alum may be added.

Example 3: Consider selective calcium carbonate removal softening of a raw water with a bar graph as drawn in the figure below. Calculate the required lime dosage as CaO, and sketch the softened water bar graph after recarbonation and filtration.

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SAB 4923 Advanced Water and Wastewater Treatment Chemical Precipitation

Split-treatment softening Dividing raw water into two portions in a two-stage system. First stage (larger portion) is given excess lime treatment Second stage is added with Na2CO3 where split flow is mixed with the treated water. Excess lime in the first stage is utilised in second stage. Advantage: reduce cost of lime and recarbonation.

Phosphorus Removal Involve precipitation with calcium, iron or aluminium. Reaction with Ca2+ produce hyroxypatite, Ca5OH(PO4)3 Precipitation is subjected to pH

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